Hard compositions of matter



' Patented July 12, 1938 2,123,576

UNITED STATES PATENT OFFICE HARD COMPOSITIONS OF MATTER Philip M. McKenna, Latrobe, Pa.

No Drawing. Original application September 6, 1935, Serial No. 39,505. Divided and this application February 24, 1937, Serial No. 127,560

5 Claims. .(Cl. 75-136) This application is a division of my pending metal or molybdenum metal, or both, and ametal application for Letters Patent, Serial No. 39,505, or metals of the iron group, in which the pro- Hard compositions of matter, filed September portion of the metals of the group including 6, 1935, upon which U. S. Patent 2,093,844 issued tungsten and molybdenum to the total non- 5 September 21, 1937, and other divisional applicarbide ingredients of the composition is subcationsare filed herewith. stantially higher than has been possible here- My invention relates to new hard compositions tofore without sacrificing strength. This is an ,of matter. It has to do, more particularly, with important feature, because an increased proporcertain novel compositions of matter, notable tion of tungsten or molybdenum, or both im- 1 for their combined strength and hardness, so parts to the hard compositions of matter the 1 that they are particularly useful in the conproperty of resisting deformation, especially at struction of tools, dies and other articles of high temperatures, but, heretofore, it has not wear-resisting or corrosion-resisting nature, as been possible to include as much tungsten or well as articles which are required to resist molybdenum as was desired, because of the deledeformation or destruction at high temperatures terious effect upon the strength of the resulting 15 and pressures. In particular, my invention recomposition.

lates to the production of new hard compositions Further objects, and obgects relating to deof matter, which are particularly useful as the tailsand economies of production and operahard bits or tips including the cutting edges of tion, will definitely appear from the detailed tools intended for cutting hard materials. These description to folloW- In o instance. I 20 compositions are also particularly adapted to use mpli h e objects f my nventi n by the d 1 as wire-drawing dies vices and means set forth in the following speci- The principal object of my invention i t profication. My invention is clearly defined and vide new hard compositions of matter, which Pointed 01115111 the ppe d d Cla shave greater combined strength, hardness and Hard compositions of matter have b known 25 resistance to deformation at high temperatures heretofore. which consisted of an amorphous and pressures any hard compositions of material, called tantalum carbide", together matter heretofore known. with certain proportions of a metal or metals of A further object of my invention is to pro- .the group nclu u g nd mo y d a0 vide new hard compositions of matter, having a a ta or metals of the group including great combined strength, hardness and resistance iron, cobalt and nickel The best of these hard to deformation, which are made from macrocompositions of m Was composed as crystalline carbides of columbium with, as a lows: Amorphous'tantalum carbide, 78 per cent, minor constituent, one or more of the carbides nickel, Per cent. tungsten, 11.8 per cent.

of the group including tantalum, titanium and This material was a e by comminutlng the 35 zirconium, which carbides are characterized, not amorphous tantalum carbide and metallic tungonly by their maro..crysta11ine form but, by a sten in a ball mill, using nickel balls, in a bath carbon content in true monatomic ratio to the of naphtha, until the mixture contained. th metals present. In other words, it is an object tantalum Carbide, tungsten and nickel in the i 40 of my invention to produce new hard composidesired degree of fineness and m the required 40 I tions of matter, having useful characteristics as proportions above nhe naphtha was then indicated, which. are made from the new macroremoved entirely by heating in a Partial V cuum crystalline product, instead of the amorphous at a red heat- Piece Was then o ed from material heretofore known, for example, as tanthis dried Powder of the desired ape d at i tnlum carbide and consisting of carburized tanpiece heated in an electric furnace, under a 45 talum, in which the carbon is not present in partial vacuum, corresponding approximately to exact monatomic ratio to the tantalum. a pressure of from 70 to 80 microns of mer- A further object of my invention is to provide cury, for forty minutes. As the result of this I novel hard compositions of matter, having great treatment, a hard composition of matter was g; .50 combined strength and hardness, which include formed having a Rockwell A" hardness of 86.5.

' titanium carbide or zirconium carbide, or both The strength of the piece thus formed is indiof them, as constituents. cated by the fact that the piece, having a thick- It is a further object of my invention to proness of .200 inch and a width of .375 inch, restvide novel hard compositions of matter, incl'uding on supports 11/16 of an inch apart, when l ing columbium carbide, together with tungsten pressed in the middle with a one centimeter 5 grams.

Another example of similar hard compositions of matter, heretofore known, is one which comprises per cent amorphous tantalum carbide, 8 per cent nickel and 12 per cent tungsten. This composition had a Rockwell A" hardness of 87.75 and broke, under the same conditions as specified above, at a load of 1500 kilograms. These two hard compositions of matter, just described, represent what I believe to be the most desirable hard compositions of this type heretofore made, known or used.

These compositions were made from a material which was called tantalum carbide, but in which the carbon was not present in exact monatomic ratio to the tantalum. This material was amorphous in character, in that it did not present crystalline form to the unaided human eye. For the purposes of this specificationI define macrocrystalline as having particles which average greater than .01 millimeter in largest cross section dimension and amorphous as having particles which average less than .01 millimeter in largest cross section dimension. I understand that there is another sense, in which all solid bodies may be described as crystalline, and may be shown to have ordered atomic arrangement by X-ray methods, or to have crystalline form which may be seen under the microscope, but I do not use the term in this sense, in this specification.

It will be observed that, in'the two compositions above-mentioned, the nickel' and tungsten together constitute 22 per cent and 20 per cent, re-

spectively, of the composition, and that the tungsten constitutes 53.6 per cent and 60 per cent, respectively, of the ingredients of the composition other than the tantalum carbide. I had believed it desirable, if possible, to increase the proportion of tungsten in the non-carbide ingredients of the composition, but I had found that this was not feasible, heretofore, because a further increase in the proportion of tungsten resulted in a decrease in the strength of the composition, which was undesirable, as the piece would break or chip when used as a metal cutting tool. Thus, although a higher percentage of tungsten is desirable, in order to give the composition increased resistance to deformation, especially at high temperatures, this increased proportion of tungsten could not be obtained, heretofore, without an accompanying decrease in the strength of the composition.

Hard compositions of matter have been proposed, heretofore, including columbium carbide, of the amorphous type in which the carbon is not present in true monatomic ratio to the columbium, together with certain proportions of tungsten and cobalt, but such hard compositions were lacking in practical value, because of theweakness of the material.

It has also been proposed, heretofore, to make hard compositions of matter from a mixture of amorphous tantalum carbide and amorphous columbium carbide, the particles of which were united into a cohesive mass by a mixture of metallic iron and molybdenum. Although such compositions were hard, they were lacking in strength as they would break under a load which was only aboutone-third of the breaking load of the amorphous tantalum carbide composition heretofore referred to.

In general, my invention consists of novel hard compositions of matter made from a macro-crystalline multicarbide of columbium, containing Brinell ball, broke under a load of 1980 kilo-- carbon in true monatomic ratio to the metals present. The macro-crystalline multicarbide forming the starting ingredient for the new composition is comminuted, in a non-oxidizing bath, as by a ball mill, for such length of time as needed to reduce the crystals to the desired degree of fineness and to incorporate in the mixture the desired proportions of a metal or metals of the group including tungsten and molybdenum, and of a metal or metals of the iron group. The powdered mixture thus formed after drying off some of the naphtha is pressed to the shape of the piece to be made, the linear dimensions, however, being from 15 to 25 per cent greater than those of the ultimate piece, depending upon the shrinkage which takes place inthe process, and the piece thus shaped is heated, under a partial vacuum, in an electric furnace, for about forty minutes at a temperature of about 1430? C. The heating should require about two hours in all, one hour and twenty minutes being consumed in gradually raising the furnace to the ultimate temperature and removing the gas and vapors, and the furnace being maintained at the ultimate temperature for about forty minutes. As a result of this treatment, the shaped piece shrinks into a cohesive bit of like shape, but smaller dimensions, and it is believed that the metal or metals of the group including tungsten and molybdenum, and the metal or metals of the iron group, included in the composition, function to unite the grains of carbide into a cohesive mass. As will be "hown hereinafter, the resulting composition has a. hardness equal to that of the compositions heretofore referred to, with a strength and resistance to deformation, especially at high temperatures, which exceeds that of said compositions.

the same", to which cross-reference is hereby made.

The invention of the present application contemplates novel hard compositions of matter embodying macro-crystalline multi-carbides of metals of the group consisting of tantalum,'

oolumbium, titanium and zirconium in which the major constituent is columbium carbide.-

My application, Serial No. 39,505, upon which U. S. Patent No. 2,093,844 issued September 21, 1937, of which this application'is a division, is now directed to compositions embodying multicarbides in which the major constituent is tantalum carbide and the minor constituent is formed by carbides of a plurality of metals of the group consisting of columbium, titanium and zirconium. Two other divisional applications of such application, Serial No. 39,505, are filed herewith, one being directed to hard compositions embodying multi-carbides in which the major constituent is tantalum carbide or columbium carbide and the minor constituent is formed by a carbide or carbides of a metal or metals of the group consisting of tantalum, columbium, titanium and zirconium. The other of such divisional applications is directed to compositions of matter embodying a macro-crystalline simple carbide, that 'is, either tantalum carbide or columbium carbide. I believe that the minor constituent of these multi-carbides is present in solid solution in the maior constituent, and this belief is confirmed by the x-ray multi-carbides. My present invention contemplates, also, new hard compositions of matter including macro-crystalline multi-carbides in which columbium carbide constitutes the major constituent, and one or more carbides of the metals of the group including tantalum, titanium and zirconium constitute the minor constituent. A study of these multi-carbides, also, has shown that the minor constituent is present in solid solution in the major constituent within certain limiting percentages of the solute. Thus, I contemplate the formation of new compositions of matter from macro-crystalline multi-carbides in which, for instance, titanium carbide or zirconium carbide, or both of them, are present in solid solution in columbium carbide, and I have found that the hard compositions of matter made from these macro-crystalline multi-carbides exhibit a very useful combination of hardness, strength and resistance to deformation. surpassing to a surprising degree anything that has been produced heretofore.

In general, the percentage of multi-carbide,

contained in my new composition is somewhat less than the percentage of columbium-carbon in the hard compositions of matter heretofore known, such as the example previously referred to, but, notwithstanding, the combined hardness, strength and resistance to deformation is greater. In general, also, in my compositions made in accordance with this invention, the

.tungsten or molybdenum, or both, constitute a greater proportion of the non-carbide ingredients of the composition than has been the case heretofore, but, nevertheless, this increase in the proportion of tungsten does not result in a weakening of the composition, but, on the contrary, a strong composition is obtained .and one having greater resistance to deformation, especially at high temperatures. This result is surprising, in view of the prior experience which led the worker in this art to believe that an increase in the proportion 01' tungsten would necessarily weaken the composition.

The following are specific examples of new compositions of matter, made in accordance with my invention, from macro-crystalline multi-carbides of the character described-in my pending application for United States Letters Patent, Serial No. 31,521. In the formulas, given in this specification, for these multi-carbides, I have included in parentheses the symbol or symbols for the metal or metals, the carbides of which form the minor constituent. It is necessary, in forming hard compositions of matter from these multi-carbides to provide other metals, which I believe perform the function of uniting the grains of inulti-carbide to form a cohesive mass and forming a matrix in which the grains of the hard carbide are embedded. These metals forming the matrix may comprise one or more of the metals of the group including tungsten and molybdenum, and one or more of the metals of the iron group. Small quantities of manganese, beryllium and aluminum may also. at times, be present with advantageous results. In general, I have found that a combination of tungsten and nickel serves. in most circumstances, to form the sort of matrix desired.

A novel hard composition of matter may be .made in accordance with my invention, using as a starting material the macro-crystalline multicarbide expressed by the formula Cb(Ti)C, in

spectograms of these which CbC constitutes the major constituent, and T10 the minor constituent. The TiC may comprise from 1 to 28 per cent of the Cb(Tl)C, the Cb(Ti)C may constitute from 40 to 82 per cent of the composition, W, from 8 to 23 per cent, and Ni, from 10 to 28 per cent. The preferred range of proportions is as follows: TiC, from 5 to 18 per cent of the Cb(Tl)C, Cb(Tl)C, from 63 to 82 per cent of the composition, W, 8 to 18 per cent. Ni, 10 to 22 per cent. A specimen of this composition, which gave desirable results, under tests, had the following specific proportions: 17.3 per cent HQ in the Cb(Tl) C, 79.78

per cent Cb('1i)C, 8.85 per cent W,v and 11.47'

per cent Ni. Tests of this specimen showed a Rockwell A" hardness of 91 and a breaking strength of 1325 kilograms. Thus, this specimen was very hard and, although it was not as strong as some compositions, I believe that the strength may be increased, without losing hardness, by increasing the tungsten content.

The specific examples of hard compositions of matter, made in accordance with my invention, just given, are illustrative of the new compositions that may be made by the use, as starting materials, of the macro-crystalline multi-carbides of the character described and claimed in my pending application for United States Letters Patent, Serial No. 31,521. It will be understood, of course, that we have not described specifically all of the possible combinations. In general molybdenum may be substituted for all or a part of the tungsten in any of these compositions, it being understood that, in making such substitution, the proportion of the metal used should be adjusted in the ratio of the atomic weights of tungsten and molybdenum. It will be understood, also, that cobalt may be substituted in whole or in part for the nickel, the proportions being adjusted in the ratiov of the atomic weights of cobalt and nickel. Iron may also be substituted for a part of the nickel or cobalt, but the fact that iron, in finely divided form, oxidizes readily, under the conditions present in making these compositions, renders its use in substitution for all or a major proportion of the nickel undesirable.

To express the range of proportions of these compositions, I prefer to state the proportions in molecular and atomic percentages of the ingredients. I prefer that the multi-carbide shall constitute from 68.1 to 55.64 molecular per cent of the composition, that a metal or metals of the group including tungsten and molybdenum should constitute from 15.58 to 17.66 atomic per cent of the composition, and that a metal or metals of the iron group shall constitute from 20.5 to 26.7 atomic per cent of the composition. I prefer, further, that, in the case of the multicarbides, the minor constituent or constituents shall constitute less than 40 molecular per cent of the multi-carbide, as this is about the maximum which will go into solid solution in the major constituent. I prefer, however, to use less than the maximum amount of minor constituent, which would go into solid solution in the major constituent, and I have determined that it is advantageous to have the minor constituent constitute about 25 per cent of the multi-carbide.

I believe that, where the carbide is columbium carbide, or a multi-carbide in which CbC is the major constituent, compositions having a better combined strength, hardness and resistance to deformation may be produced by substituting molybdenum, in whole or in part. for the Mgsten. I

The preferred methods for making these new compositions of matter are described in detail and claimed in my pending application for Letters Patent, Serial No. 66,707, Method of producing hard compositions of matter, which likewise is a division of my pending application for Letters Patent, Serial No. 395,505, Hard compositions of matter, filed September 6, 1935, of which the present application is a division. Consequently, the various steps will not be described in detail herein.

In general, the macro-crystalline multi-carbide is ground and comminuted in a ball mill with metallic tungsten or molybdenum and with nickel, cobalt or iron, the comminution with the metallic ingredients being continued until the ingredients reach the desired state of fineness and until they are present in the proper proportions. The comminution is preferably carried out in a bath of naphtha, or other suitable material, to prevent oxidation, and it is preferable that the.

naphtha be previously purified, as by subjecting it to freshly cut surfaces of sodium, to remove oxygen and sulphur-containing compounds.

The finely comminuted particles are partially dried, 1 to 5 per centof the naphtha being left to protect the powder from oxidation, and the thoroughly mixed particles are then pressed into bits of the desired shape and of a size such as to compensate for the shrinkage of 15 to 25 per cent which will later take place in the heat treatment. The bits are then subjected to heat treatment under a vacuum of from 40 to 7 microns of mercury pressure, in an electric furnace, for about forty minutes at a temperature of from 1400 C. to 1500" 0., depending upon the ratio of the metals, the temperature being slowly raised until it reaches this temperature. The vacuum is obtained by a Gaede mercury diffusing pump which draws off and absorbs gases and vapors, including the vapors coming from the hydrocarbon, and the outlet of the mercury diffusion pump is connected to an oil pump. The bits are I preferably heated in an electric induction furnace, being placed within a covered graphite crucible.

I believe that one reason for the good characteristics of hard compositions of matter, which have as an ingredient a comminuted macro-crystalline multi-carbide including TiC or ZrC, is that, when the T10 or ZrC, or both of them, are in solid solution in the CbC, they are capable of treatment by processes of powder metallurgy, which would destroy their surfaces when present alone, in the form of the chemically simple ZrC or TiC. That is to say, the Chi), in which the ZrC or TiC is dissolved, keeps it from being oxidized or otherwise reacted upon, during the grinding and heat treatments. Indicative of this is the fact that TiC and ZrC, per se, cannot be prepared by the method used to produce macrocrystalline TaC, but, when prepared in solid solution in CbC, they can be treated with acid, and dried-with air,and preserve an exact monatomic ratio ofcarbon to metal.

Another reason for the great utility of the hard compositions of matter, macro-crystalline multi-carbide as an ingredient, is that such multi-carbides are harder than the simple carbides, following the generalization that all solid solutions are harder than their simple components. This effect is fundamental and 1 particles including a comminuted tors. This is an advantage when the composition is used in certain kinds of drawing dies and tools, for, in these cases, a greater proportion of the heat, generated by mechanical work at the point of contact, is distributed to the piece on which the work is done.

Whenever I use the term "macro-crystalline in the appended claims, with reference to a carbide or multi-carbide, I mean a carbide having which average greater than .01 millimeter in largest cross section dimension and produced by the reaction between a metal or metals and carbon in the presence of a menstruum other than the reactants.

I am aware that the products herein disclosedmay be varied considerably, without departing from the spirit of my invention, and, therefore, I claim my invention broadly as indicated by the appended claims.

What I claim is: I

1. The new hard composition of matter consisting substantially of a matrix formed of an alloy of a metal of the group consisting of tungsten and molybdenum with a metal of the iron group, in which there are embedded particles of a comminuted macro-crystalline multi-carbide consisting of a minor proportion of a carbide of a metal of the group consisting of titanium and zirconium in solid solution in a major proportion of columbium carbide, said particles constituting the major portion of said hard composition of matter.

2. The new hard composition of matter consisting substantially of a matrix formed of an alloy of a metal of the group consisting of tungsten and molybdenum with a metal of the iron group, in which there are embedded particles of a comminuted macro-crystalline multi-carbide consisting of titanium carbide'in solid solution in columbium carbide, said titanium carbide being in an amount less than 40 molecular per cent of said multi-carbide.

3. The new hard composition of matter consistingsubstantially of a matrix formed of an alloy of a metal of the group consisting of tungsten and molybdenum with a metal of the iron group, in which there are embedded particles of a comminuted macro-crystalline multi-carbide having from 5 to 18 per cent of titanium carbide in solid solution in columbium carbide, said particles constituting the major portion of said hard composition of matter.

4. The new hard composition of matter consisting substantially of from 8 to 18 per cent tungsten, from 10 to 22 per cent nickel, and from 63 to 82 per cent of a comminuted macrocrystalline multi-carbide having columbium carbide as its major constituent and including from 5 to -l8 per cent titanium carbide.

5. The new hard composition of matter, consisting substantially of about 9 per cent tungsten, about 11 per cent nickel, and about per cent of a comminuted macro-crystalline multicarbide consisting of about 17 per cent titanium carbide in solid solution in columbium carbide.

PHILIP M. .McKENNA. 

